WO2020181754A1 - Treatment system and treatment process for removing hardness, silicon, and turbidity from wastewater having high salt concentration - Google Patents

Treatment system and treatment process for removing hardness, silicon, and turbidity from wastewater having high salt concentration Download PDF

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Publication number
WO2020181754A1
WO2020181754A1 PCT/CN2019/106691 CN2019106691W WO2020181754A1 WO 2020181754 A1 WO2020181754 A1 WO 2020181754A1 CN 2019106691 W CN2019106691 W CN 2019106691W WO 2020181754 A1 WO2020181754 A1 WO 2020181754A1
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Prior art keywords
membrane
tank
silicon
turbidity
reaction
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French (fr)
Chinese (zh)
Inventor
张承慈
葛文越
程新燕
钱勇
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Keysino Separation Technology Inc
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Keysino Separation Technology Inc
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Priority to US17/260,556 priority Critical patent/US20210261447A1/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2642—Aggregation, sedimentation, flocculation, precipitation or coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/04—Elements in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/04—Backflushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/162—Use of acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Definitions

  • the invention relates to a water treatment process, in particular to a treatment system and treatment process for removing hard, silicon and turbidity from high-salt wastewater.
  • High-salt wastewater has the characteristics of high salt content, high hardness and high silicon. If it is not disposed and used reasonably, it will not only waste water resources, but also cause serious environmental pollution. Therefore, the development of efficient, low-consumption, safe and economical water treatment technology is an inevitable trend in the development of modern water treatment technology.
  • the treatment of high-salt wastewater mostly adopts the treatment method of "membrane concentration + evaporation and crystallization".
  • the high concentration of calcium, magnesium ions and silicon dioxide in the waste water is easy to scale and cause membrane pollution, which seriously affects the stable operation of the system, increases labor intensity and operating costs, and severely limits the enterprise's high-salt wastewater treatment capacity. Therefore, in order to ensure the normal operation of subsequent membrane concentration, it is necessary to remove calcium, magnesium and silica in wastewater by chemical dosing methods. After chemical dosing, it needs to undergo solid-liquid separation pretreatment before entering the membrane concentration process. The pretreatment effect will directly affect the efficiency and life of membrane concentration.
  • the traditional pretreatment process is "clarification tank + ultrafiltration membrane filtration", which removes most of the solid particles through the static precipitation of the clarification tank, and then removes the remaining suspended solids in the water by the ultrafiltration membrane, so that the water quality reaches the reverse osmosis inflow Claim.
  • the hardness of the influent water and the content of silicon are different.
  • the particle size of the sludge produced (calcium carbonate sludge, magnesium hydroxide sludge, silicate sludge) is different, and the sedimentation time of the sludge is different. The difference in residence time leads to a longer time-consuming process.
  • Chinese patent CN108751523A discloses a method of directly filtering high-salt wastewater after the dosing reaction with a tubular membrane device. Although this method saves the floor space and sedimentation time of the clarifier, the tubular membrane device has high energy consumption and It covers a large area.
  • the purpose of the present invention is to provide a treatment system and process for removing hard and silicon and turbidity from high-salt wastewater in order to overcome the above-mentioned defects in the prior art.
  • the invention has short process flow, small land occupation, low energy consumption and stable operation, can efficiently remove the hardness and silicon content in high-salt wastewater, and ensures the stability of the subsequent high-salt wastewater membrane concentration treatment process.
  • a treatment system for removing hard, silicon, and turbidity in high-salt wastewater comprising an integrated reaction device and a membrane separation device.
  • the integrated reaction device includes a reaction box and a dosing device for adding medicament to the reaction box.
  • the separation device includes a membrane tank, a membrane module installed in the membrane tank for separating the mixed liquid from the reaction tank, and a water production pipeline leading from the membrane tank.
  • a water production pump is installed on the water production pipeline. The connection between the tanks is used to make the mixed solution after adding the drug reaction in the reaction box directly enter the membrane tank water inlet pipeline of the membrane tank, and the membrane tank water inlet pump is arranged on the membrane tank water inlet pipeline.
  • the reaction box has a built-in baffle to divide the inside of the reaction box into a plurality of dosing compartments.
  • the baffles are arranged in a staggered arrangement in the reaction box to form a solution that can make the solution react.
  • the up and down channels in the vessel are arranged in a staggered arrangement in the reaction box to form a solution that can make the solution react.
  • the dosing compartment includes but is not limited to the softening agent dosing room and the silicon removal agent dosing room.
  • a stirrer is arranged in the reaction box, and a reaction box mud pump is arranged at the bottom of the reaction box.
  • one or more groups of membrane modules are arranged in the membrane tank.
  • the material of the membrane module is polytetrafluoroethylene (PTFE), which has good acid and alkali resistance, and can withstand long-term operation in the range of pH 1-14. There is no need to adjust the pH after chemical dosing, and it can directly contact the membrane element; at the same time, it can withstand the immersion of sodium hypochlorite solution within 3000ppm. There is no requirement for chloride ion concentration and there is no chloride ion corrosion problem.
  • PTFE polytetrafluoroethylene
  • the pore diameter of the membrane module is 0.01-0.5 ⁇ m, and different pore diameter ranges can be selected according to requirements, which can meet the requirements for the use of various particle diameters.
  • the membrane pore size is in the range of 0.01 ⁇ 0.5um, which is far smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than the particles of chelate produced by calcium magnesium silicate Therefore, the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) and the influence of water quality fluctuations on the precipitation The impact of particles.
  • the form of the membrane module includes, but is not limited to, plate type, tube type, hollow fiber, roll type and the like.
  • an aeration device and a sludge pump of the membrane tank are provided at the bottom of the membrane tank.
  • the aeration device is mainly used for mixing and stirring, so that the sludge in the membrane tank is in a suspended state with a uniform concentration and does not deposit on the membrane surface. At the same time, it flushes the membrane surface to prevent membrane pollution.
  • a backwash system and a chemical cleaning system are provided on the water production pipeline, and the backwash system includes a backwash water tank and a backwash pipeline between the backwash water tank and the water production pipeline
  • a backwash pump is provided on the backwash pipeline
  • the chemical cleaning system includes equipment such as acid metering tank, acid dosing pump, alkali metering tank, alkali dosing pump, sodium hypochlorite metering box, and sodium hypochlorite dosing pump.
  • the backwash water in the backwash water tank enters the membrane separation device through the backwash pump to clean the membrane to ensure the separation efficiency of the membrane.
  • the water in the backwash water tank can be produced water or a certain acid, alkali and sodium hypochlorite solution can be regularly prepared for backwashing.
  • the invention also provides a treatment process for removing hard, silicon and turbidity of high-salt wastewater based on the treatment system, which includes the following steps:
  • the high-salt wastewater enters the reaction tank.
  • the required reagents are added to the wastewater through the dosing device.
  • the reagents and wastewater are fully mixed and reacted to produce different types of sludge particles, including but not limited to carbonic acid.
  • the sludge particle mixture directly enters the membrane tank; it is in a suspended state and uniform concentration under the action of the aeration device.
  • the membrane module is screened and filtered, the produced water is discharged from the membrane tank through the production pump, and the intercepted sludge particles pass through the membrane.
  • the pool sludge pump discharges the membrane pool; the membrane separation device uses the principle of sieving and filtration to directly trap the sludge particles of the mixed liquid on the outside of the membrane filaments, and the produced water is recycled and used, and the sludge particles are discharged out of the membrane separation device.
  • the produced water meets the requirement of reverse osmosis water inflow.
  • the required agents include but are not limited to softening agents and silicon removal agents, and the softening agents include lime, sodium hydroxide, sodium carbonate and the like.
  • the treatment process adopts a continuous water inlet and outlet mode, and an operation mode of continuous mud discharge or intermittent mud discharge.
  • the functions of the main devices are as follows:
  • Reaction box wastewater and chemical reaction zone
  • Dosing device According to the wastewater quality and the requirements of turbidity removal, hardness removal and silicon removal, a certain concentration of medicaments, such as lime, NaOH, Na 2 CO 3 and magnesium reagents, are prepared.
  • medicaments such as lime, NaOH, Na 2 CO 3 and magnesium reagents
  • Reaction box mud pump quantitatively discharge mud to keep the wastewater suspended solids (SS) concentration in the membrane filtration zone stable.
  • Mixer fully mix waste water and medicament to ensure the removal rate of calcium, magnesium and silicon.
  • Membrane tank inlet pump the wastewater after the dosing reaction enters the membrane filtration device quantitatively.
  • Membrane tank membrane filtration device area
  • Membrane module Solid-liquid separation is performed on the wastewater after the dosing reaction to ensure that the effluent reaches the reverse osmosis influent water quality.
  • Aeration device to ensure uniform concentration of wastewater in the membrane filtration area; flush the membrane surface to prevent membrane pollution.
  • Membrane tank sludge pump The sludge particles trapped by the membrane module are discharged from the membrane tank.
  • Water production pump Provides transmembrane pressure difference and quantitatively discharges water.
  • Backwash water tank a certain concentration of backwash water can be prepared regularly.
  • Backwash pump Backwash the membrane module with water in the backwash tank.
  • Cleaning system cleaning membrane components.
  • the process of the present invention adopts a combination of an integrated reaction device and a membrane separation device, and is applied to the softening and hardening of high salt water, and the process flow is small.
  • the traditional process generally uses a combination of mixed reaction + precipitation + coarse filtration (sand filtration) + ultra (micro) filtration.
  • the process of the present invention is greatly simplified compared with the traditional process, does not need to consider the sedimentation and separation of sludge and multi-stage filtration, has less equipment, small floor space, short construction period and low investment cost.
  • the process of the present invention uses the filtering sieving mechanism for solid-liquid separation, directly trapping the particles generated by the reaction on the outside of the membrane filament, without considering the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) And the impact of water quality fluctuations on the precipitated particles, the process operation is more stable.
  • the process of the present invention can efficiently remove the hardness and silicon content in high-salt wastewater, has low energy consumption, and consumes 0.8-1KWH of water and electricity per ton of treatment.
  • the combined process of traditional mixing reaction + precipitation + filtration (sand filtration) + ultra (micro) filtration consumes 1.5 KWH of water and electricity per ton, and the operating energy consumption also has greater advantages.
  • the membrane selected in the present invention has the following two characteristics: 1
  • the membrane element is made of PTFE, which has good acid and alkali resistance, and can operate in any range of pH 1-14, and there is no need to call back after chemical dosing pH, can directly contact the membrane element; there is no requirement for chloride ion concentration, and there is no chloride ion corrosion problem.
  • the pore size of the membrane is in the range of 0.01 ⁇ 0.5um, which is much smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than that of chelate produced by calcium magnesium silicate. Particle diameter, so the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time and water quality fluctuations in the traditional softening process (reaction-precipitation-filtration-ultrafiltration). The impact of sedimentation particles.
  • Fig. 1 is a schematic diagram of the structure of a treatment system for removing hard, silicon and turbidity of high-salt wastewater in Example 1 of the present invention.
  • reaction tank 1 reaction tank; 2 dosing device; 3 reaction tank mud pump; 4 mixer; 5 membrane tank inlet pump; 6 membrane tank; 7 membrane module; 8 aeration device; 9 membrane tank mud pump; 10 production water pump; 11 Backwash water tank; 12 backwash pump; 13 chemical cleaning system.
  • a treatment system for removing hard, silicon, and turbidity of high-salt wastewater includes an integrated reaction device and a membrane separation device.
  • the integrated reaction device includes a reaction box 1, and is used for adding chemicals to the reaction box 1.
  • Medicine device 2 the membrane separation device includes a membrane tank 6, a membrane module 7 arranged in the membrane tank 6 for separating the mixed liquid from the reaction tank 1, and a water production line drawn from the membrane tank 6, in production
  • the water production pump 10 is installed on the water pipeline, and is connected between the reaction tank 1 and the membrane tank 6 to make the mixed liquid after adding the chemical reaction in the reaction tank 1 directly enter the membrane tank water inlet pipeline of the membrane tank 6, and enter the membrane tank
  • a membrane tank inlet pump 5 is set on the water pipeline.
  • the reaction box 1 has a built-in baffle, which divides the inside of the reaction box 1 into a plurality of dosing compartments.
  • the baffles are arranged in a staggered arrangement in the reaction box 1 so that the solution can move up and down in the reactor. Baffled channel.
  • the dosing compartment includes but is not limited to the softening agent dosing room and the silicon removal agent dosing room.
  • a stirrer 4 is provided in the reaction box 1, and a reaction box mud pump 3 is provided at the bottom of the reaction box 1.
  • one or more sets of membrane modules 7 in the membrane tank 6 are provided.
  • the material of the membrane component 7 is polytetrafluoroethylene (PTFE), which has good acid and alkali resistance, and can withstand long-term operation in the range of pH 1-14. There is no need for chemical dosing. Adjusting the pH, it can directly contact the membrane element; at the same time, it can withstand the immersion of sodium hypochlorite solution within 3000ppm. There is no requirement for chloride ion concentration and there is no chloride ion corrosion problem.
  • PTFE polytetrafluoroethylene
  • the pore size of the membrane module 7 is 0.01-0.5 ⁇ m, and an unfair pore size range is selected according to requirements, which can meet the requirements for the use of various particle sizes.
  • the membrane pore size is in the range of 0.01 ⁇ 0.5um, which is far smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than the particles of chelate produced by calcium magnesium silicate Therefore, the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) and the influence of water quality fluctuations on the precipitation The impact of particles.
  • the form of the membrane module 7 includes, but is not limited to, a plate type, a tube type, a hollow fiber, a roll type, and the like.
  • the bottom of the membrane tank 6 is provided with an aeration device 8 and a membrane tank mud pump 9.
  • the aeration device 8 is mainly used for mixing and stirring, so that the sludge in the membrane tank 6 is in a suspended state, with a uniform concentration, and does not deposit on the membrane surface, while scouring the membrane surface to prevent membrane pollution.
  • a backwash system and a chemical cleaning system are provided on the water production pipeline.
  • the backwash system includes a backwash water tank 11 and a backwash pipeline between the backwash water tank 11 and the water production pipeline.
  • a backwash pump 12 is provided on the backwash pipeline;
  • the chemical cleaning system includes acid metering tank, acid dosing pump, alkali metering box, alkali dosing pump, sodium hypochlorite metering box, sodium hypochlorite dosing pump and other equipment.
  • the backwash water in the backwash water tank enters the membrane separation device through the backwash pump to clean the membrane to ensure the separation efficiency of the membrane.
  • the water in the backwash water tank can be produced water or a certain acid, alkali and sodium hypochlorite solution can be regularly prepared for backwashing.
  • This embodiment also provides a treatment process for removing hard, silicon and turbidity from high-salt wastewater based on the treatment system, which includes the following steps:
  • the high-salt wastewater enters the reaction tank 1.
  • the required agent is added to the wastewater through the dosing device 2.
  • the agent and the wastewater are fully mixed and reacted to produce different types of sludge particles, including but not only Limited to calcium carbonate sludge, magnesium hydroxide sludge, silicate sludge, and then remove the hardness, silica, turbidity, etc. in the wastewater;
  • the sludge particle mixture directly enters the membrane tank 6; it is suspended and uniform in concentration under the action of the aeration device.
  • the produced water is discharged from the membrane tank 6 through the production water pump 10, and the trapped sewage
  • the sludge particles are discharged from the membrane tank 6 through the membrane tank sludge pump 9; the membrane separation device uses the principle of sieving and filtration to directly trap the sludge particles of the mixed liquid on the outside of the membrane filaments, the produced water is recycled and used, and the sludge particles are discharged outside Membrane separation device.
  • the produced water meets the requirement of reverse osmosis water inflow.
  • the required agents include, but are not limited to, softening agents and silicon removal agents, and the softening agents include lime, sodium hydroxide, sodium carbonate and the like.
  • the treatment process adopts a continuous water inlet and outlet mode, and an operation mode of continuous sludge discharge or intermittent sludge discharge.
  • the high-salt wastewater of a coal chemical industry has TDS content of 35000mg/L, SiO 2 concentration of 80mg/L, and hardness of about 5mmol/L. It belongs to high-salt, high-silicon, and high-hardness wastewater.
  • the influent SS concentration is 1.2 ⁇ 2.5g/L
  • the SS concentration of wastewater in the membrane filtration zone is concentrated to 15.5 ⁇ 33g/L
  • the concentration factor is 10. ⁇ 20 times.
  • the SiO 2 in the product water is less than 18mg/L, the hardness is less than 0.5mmol/L, the SDI is maintained at 3 to 5, and the turbidity is less than 1NTU, and the product water can be directly fed into the subsequent reverse osmosis treatment process.
  • the content of TDS in a certain high-salt wastewater is 45000mg/L, the concentration of SiO 2 is 150mg/L, and the hardness is about 8mmol/L. It belongs to high-salt, high-silicon, and high-hardness wastewater.
  • the water produced After using the high-salt wastewater in Example 1 to remove hard and silicon and remove turbidity, the water produced has SiO 2 ⁇ 15 mg/L, low hardness, SDI range of 3 to 4, and turbidity ⁇ 0.5NTU.
  • the product water enters the subsequent reverse osmosis treatment process, the operating stability of the reverse osmosis system is good, and the cleaning cycle is stable> 1.5 months.
  • the TDS content in a certain high-salt wastewater is 50000mg/L, the SiO 2 concentration is 400mg/L, and the hardness is about 10mmol/L. It belongs to high-salt, high-silicon and high-hardness wastewater.
  • the SiO 2 of the produced water wastewater is less than 30 mg/L, the hardness is less than 0.8 mmol/L, the SDI is less than or equal to 5, and the turbidity remains below 0.5 NTU.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A treatment system for removing hardness, silicon, and turbidity from wastewater having a high salt concentration, comprising an integrated reaction apparatus and a membrane separation apparatus, wherein the integrated reaction apparatus comprises a reaction box (1) and a chemical drug adding device (2); the membrane separation apparatus comprises a membrane pool (6) and a membrane component (7). The wastewater having the high salt concentration enters the reaction box (1); a required chemical drug is added to the wastewater by means of the chemical drug adding device (2); the chemical drug and the wastewater are fully mixed and react to produce different kinds of sludge particles; a sludge particle mixed liquid directly enters the membrane pool (6); under the action of an aeration device (8), sludge is in a suspension state and uniform in concentration, and is screened and filtered by the membrane component (7); produced water is discharged from the membrane pool (6), and intercepted sludge particles are discharged from the membrane pool (6). Also disclosed is a treatment process for removing hardness, silicon, and turbidity from wastewater having a high salt concentration.

Description

一种高盐废水除硬除硅除浊的处理系统与处理工艺Treatment system and treatment process for removing hard, silicon and turbidity of high-salt wastewater 技术领域Technical field

本发明涉及水处理工艺，尤其是涉及一种高盐废水除硬除硅除浊的处理系统与处理工艺。The invention relates to a water treatment process, in particular to a treatment system and treatment process for removing hard, silicon and turbidity from high-salt wastewater.

背景技术Background technique

高盐废水具有高含盐量、高硬度和高硅等特点，若不合理处置及利用，不但会浪费水资源，而且会造成严重的环境污染。所以，研发高效、低耗、安全、经济的水处理工艺是发展现代水处理技术的必然趋势。High-salt wastewater has the characteristics of high salt content, high hardness and high silicon. If it is not disposed and used reasonably, it will not only waste water resources, but also cause serious environmental pollution. Therefore, the development of efficient, low-consumption, safe and economical water treatment technology is an inevitable trend in the development of modern water treatment technology.

高盐废水处理多采用“膜浓缩+蒸发结晶”的处理方法。而废水中的钙镁离子和二氧化硅浓度较高，易结垢造成膜污染，严重影响系统的稳定运行，增加劳动强度以及运行费用，严重限制了企业的高含盐废水处理能力。因此，为保证后续膜浓缩的正常运行，需要通过化学加药的方法去除废水中的钙镁和二氧化硅。在进行化学加药后，需经过固液分离预处理方可进入膜浓缩工艺。预处理效果的好坏将直接影响膜浓缩的效率和寿命。The treatment of high-salt wastewater mostly adopts the treatment method of "membrane concentration + evaporation and crystallization". The high concentration of calcium, magnesium ions and silicon dioxide in the waste water is easy to scale and cause membrane pollution, which seriously affects the stable operation of the system, increases labor intensity and operating costs, and severely limits the enterprise's high-salt wastewater treatment capacity. Therefore, in order to ensure the normal operation of subsequent membrane concentration, it is necessary to remove calcium, magnesium and silica in wastewater by chemical dosing methods. After chemical dosing, it needs to undergo solid-liquid separation pretreatment before entering the membrane concentration process. The pretreatment effect will directly affect the efficiency and life of membrane concentration.

目前，传统的预处理工艺是“澄清池+超滤膜过滤”，经过澄清池的静置沉淀去除大部分固体颗粒，然后由超滤膜去除水中剩余悬浮固体，从而使水质达到反渗透进水要求。但进水水质的硬度、硅等的含量不同，产生污泥(碳酸钙污泥、氢氧化镁污泥、硅酸盐污泥)的颗粒大小不同，污泥所需沉淀时间不同，污泥的停留时间不同导致了此工艺耗时较长。由于进水水质的波动，此工艺在多数项目运行中易出现翻池等现象，沉淀效果较差，导致了整个工艺运行的抗波动性和稳定性较差。传统工艺耗时长、占地面积大、成本高、抗波动性和稳定性差。中国专利CN108751523A披露了一种直接以管式膜装置过滤加药反应后的高盐废水的方法，此方法虽然省去了澄清池的占地面积和沉淀时间，但是管式膜装置能耗高且占地面积较大。At present, the traditional pretreatment process is "clarification tank + ultrafiltration membrane filtration", which removes most of the solid particles through the static precipitation of the clarification tank, and then removes the remaining suspended solids in the water by the ultrafiltration membrane, so that the water quality reaches the reverse osmosis inflow Claim. However, the hardness of the influent water and the content of silicon are different. The particle size of the sludge produced (calcium carbonate sludge, magnesium hydroxide sludge, silicate sludge) is different, and the sedimentation time of the sludge is different. The difference in residence time leads to a longer time-consuming process. Due to the fluctuation of influent water quality, this process is prone to phenomenon such as pool turning in most projects, and the precipitation effect is poor, resulting in poor resistance to fluctuations and stability of the entire process operation. The traditional process takes a long time, covers a large area, high cost, and has poor resistance to fluctuations and stability. Chinese patent CN108751523A discloses a method of directly filtering high-salt wastewater after the dosing reaction with a tubular membrane device. Although this method saves the floor space and sedimentation time of the clarifier, the tubular membrane device has high energy consumption and It covers a large area.

鉴于此，特提出本发明。In view of this, the present invention is proposed.

发明内容Summary of the invention

本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种高盐废水除 硬除硅除浊的处理系统与处理工艺。The purpose of the present invention is to provide a treatment system and process for removing hard and silicon and turbidity from high-salt wastewater in order to overcome the above-mentioned defects in the prior art.

本发明工艺流程短、占地小、能耗低、运行稳定，可以高效去除高盐废水中的硬度及硅含量，保证后续高盐废水膜浓缩处理工艺的稳定性。The invention has short process flow, small land occupation, low energy consumption and stable operation, can efficiently remove the hardness and silicon content in high-salt wastewater, and ensures the stability of the subsequent high-salt wastewater membrane concentration treatment process.

本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:

一种高盐废水除硬除硅除浊的处理系统，包括一体化反应装置和膜分离装置，所述一体化反应装置包括反应箱、用于向反应箱加入药剂的加药装置，所述膜分离装置包括膜池、设置在膜池中用于对来自反应箱的混合液进行分离的膜组件，以及从膜池引出的产水管线，在产水管线上设置产水泵，在反应箱与膜池之间连接用于使反应箱中加入药剂反应后的混合液直接进入到膜池的膜池进水管线，在膜池进水管线上设置膜池进水泵。A treatment system for removing hard, silicon, and turbidity in high-salt wastewater, comprising an integrated reaction device and a membrane separation device. The integrated reaction device includes a reaction box and a dosing device for adding medicament to the reaction box. The separation device includes a membrane tank, a membrane module installed in the membrane tank for separating the mixed liquid from the reaction tank, and a water production pipeline leading from the membrane tank. A water production pump is installed on the water production pipeline. The connection between the tanks is used to make the mixed solution after adding the drug reaction in the reaction box directly enter the membrane tank water inlet pipeline of the membrane tank, and the membrane tank water inlet pump is arranged on the membrane tank water inlet pipeline.

在本发明的其中一个优选实施方式中，所述反应箱内置挡板，将反应箱内部分隔成多个加药隔间，所述挡板在反应箱内高低交错排列，形成可以使溶液在反应器内上下折流的通道。In one of the preferred embodiments of the present invention, the reaction box has a built-in baffle to divide the inside of the reaction box into a plurality of dosing compartments. The baffles are arranged in a staggered arrangement in the reaction box to form a solution that can make the solution react. The up and down channels in the vessel.

加药隔间包括但不仅限于软化药剂加药间、除硅剂加药间。The dosing compartment includes but is not limited to the softening agent dosing room and the silicon removal agent dosing room.

在本发明的其中一个优选实施方式中，所述反应箱内设置搅拌机，在反应箱底部设置反应箱排泥泵。In one of the preferred embodiments of the present invention, a stirrer is arranged in the reaction box, and a reaction box mud pump is arranged at the bottom of the reaction box.

在本发明的其中一个优选实施方式中，所述膜池内的膜组件设置一组或多组。In one of the preferred embodiments of the present invention, one or more groups of membrane modules are arranged in the membrane tank.

在本发明的其中一个优选实施方式中，所述膜组件的材质为聚四氟乙烯(PTFE)，具有很好的耐酸性和耐碱性，可以耐受pH为1-14的范围长期运行，化学加药后无需回调pH，可以直接与膜元件接触；同时可以耐受3000ppm以内的次氯酸钠溶液的浸泡。对氯离子浓度无要求，不存在氯离子腐蚀问题。In one of the preferred embodiments of the present invention, the material of the membrane module is polytetrafluoroethylene (PTFE), which has good acid and alkali resistance, and can withstand long-term operation in the range of pH 1-14. There is no need to adjust the pH after chemical dosing, and it can directly contact the membrane element; at the same time, it can withstand the immersion of sodium hypochlorite solution within 3000ppm. There is no requirement for chloride ion concentration and there is no chloride ion corrosion problem.

在本发明的其中一个优选实施方式中，所述膜组件孔径为0.01-0.5μm，根据需求选择不同的孔径范围，可以满足多种不同颗粒物粒径的使用要求。膜孔径为0.01～0.5um的范围，远远小于软化生成的碳酸钙(20um以上)和氢氧化镁颗粒直径(1-5um)，远远小于钙镁硅酸盐所生成的螯合物的颗粒直径，因此可以利用筛分过滤的原理，直接将反应生成的颗粒物截留在膜丝外侧，不需要考虑传统软化工艺(反应-沉淀-过滤-超滤)中沉淀分离的沉降时间及水质波动对沉淀颗粒的影响。In one of the preferred embodiments of the present invention, the pore diameter of the membrane module is 0.01-0.5 μm, and different pore diameter ranges can be selected according to requirements, which can meet the requirements for the use of various particle diameters. The membrane pore size is in the range of 0.01～0.5um, which is far smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than the particles of chelate produced by calcium magnesium silicate Therefore, the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) and the influence of water quality fluctuations on the precipitation The impact of particles.

在本发明的其中一个优选实施方式中，所述膜组件的形式包括但不仅限于板式、管式、中空纤维、卷式等。In one of the preferred embodiments of the present invention, the form of the membrane module includes, but is not limited to, plate type, tube type, hollow fiber, roll type and the like.

在本发明的其中一个优选实施方式中，所述膜池底部设置曝气装置与膜池排泥 泵。曝气装置主要是混合搅拌作用，使膜池内污泥处于悬浮状态，浓度均匀，不沉积在膜表面，同时冲刷膜表面，防止膜污染。In one of the preferred embodiments of the present invention, an aeration device and a sludge pump of the membrane tank are provided at the bottom of the membrane tank. The aeration device is mainly used for mixing and stirring, so that the sludge in the membrane tank is in a suspended state with a uniform concentration and does not deposit on the membrane surface. At the same time, it flushes the membrane surface to prevent membrane pollution.

在本发明的其中一个优选实施方式中，在所述产水管线上设置反洗系统与化学清洗系统，所述反洗系统包括反洗水箱以及反洗水箱与产水管线之间的反洗管线，在所述反洗管线上设置反洗泵；所述化学清洗系统包括酸计量箱、酸加药泵、碱计量箱、碱加药泵、次氯酸钠计量箱、次氯酸钠加药泵等设备。所述反洗水箱中的反洗水经过反洗泵进入到膜分离装置对膜进行清洗，以保证膜的分离效率。根据需要，反洗水箱中的水可以是产水或者定期配制一定酸、碱和次氯酸钠溶液等进行反洗。In one of the preferred embodiments of the present invention, a backwash system and a chemical cleaning system are provided on the water production pipeline, and the backwash system includes a backwash water tank and a backwash pipeline between the backwash water tank and the water production pipeline A backwash pump is provided on the backwash pipeline; the chemical cleaning system includes equipment such as acid metering tank, acid dosing pump, alkali metering tank, alkali dosing pump, sodium hypochlorite metering box, and sodium hypochlorite dosing pump. The backwash water in the backwash water tank enters the membrane separation device through the backwash pump to clean the membrane to ensure the separation efficiency of the membrane. According to needs, the water in the backwash water tank can be produced water or a certain acid, alkali and sodium hypochlorite solution can be regularly prepared for backwashing.

本发明还提供基于所述处理系统进行高盐废水除硬除硅除浊的处理工艺，包括以下步骤：The invention also provides a treatment process for removing hard, silicon and turbidity of high-salt wastewater based on the treatment system, which includes the following steps:

高盐废水进入反应箱，根据废水水质和产水要求，通过加药装置在废水中加入所需药剂，在搅拌作用下药剂与废水充分混合反应产生不同种类的污泥颗粒，包括但不仅限于碳酸钙污泥、氢氧化镁污泥、硅酸盐污泥，进而去除废水中的硬度、二氧化硅、浊度等；The high-salt wastewater enters the reaction tank. According to the requirements of wastewater quality and product water, the required reagents are added to the wastewater through the dosing device. Under stirring, the reagents and wastewater are fully mixed and reacted to produce different types of sludge particles, including but not limited to carbonic acid. Calcium sludge, magnesium hydroxide sludge, silicate sludge, and then remove the hardness, silica, turbidity, etc. in the wastewater;

污泥颗粒混合液直接进入到膜池中；在曝气装置的作用下处于悬浮状态、浓度均匀，经过膜组件的筛分过滤，产水经产水泵排出膜池，截留的污泥颗粒经过膜池排泥泵排出膜池；所述膜分离装置利用筛分过滤的原理，直接将混合液的污泥颗粒物截留在膜丝外侧，产水回收利用，污泥颗粒外排出膜分离装置。The sludge particle mixture directly enters the membrane tank; it is in a suspended state and uniform concentration under the action of the aeration device. After the membrane module is screened and filtered, the produced water is discharged from the membrane tank through the production pump, and the intercepted sludge particles pass through the membrane. The pool sludge pump discharges the membrane pool; the membrane separation device uses the principle of sieving and filtration to directly trap the sludge particles of the mixed liquid on the outside of the membrane filaments, and the produced water is recycled and used, and the sludge particles are discharged out of the membrane separation device.

其中，所述产水满足反渗透进水的要求。Wherein, the produced water meets the requirement of reverse osmosis water inflow.

在本发明的其中一个优选实施方式中，所需药剂包括但不仅限于软化药剂、除硅剂，所述软化药剂包括石灰、氢氧化钠、碳酸钠等。In one of the preferred embodiments of the present invention, the required agents include but are not limited to softening agents and silicon removal agents, and the softening agents include lime, sodium hydroxide, sodium carbonate and the like.

在本发明的其中一个优选实施方式中，所述处理工艺采用连续进出水方式，采用连续排泥或间歇排泥的运行方式。In one of the preferred embodiments of the present invention, the treatment process adopts a continuous water inlet and outlet mode, and an operation mode of continuous mud discharge or intermittent mud discharge.

本发明中，主要装置的作用如下，In the present invention, the functions of the main devices are as follows:

1、反应箱：废水与药剂反应区1. Reaction box: wastewater and chemical reaction zone

2、加药装置：根据废水的水质和除浊、除硬度以及除硅的要求配制一定浓度的药剂，如：石灰、NaOH、Na 2CO 3和镁剂等所需的各类药剂。 2. Dosing device: According to the wastewater quality and the requirements of turbidity removal, hardness removal and silicon removal, a certain concentration of medicaments, such as lime, NaOH, Na 2 CO 3 and magnesium reagents, are prepared.

3、反应箱排泥泵：定量排泥，使膜过滤区的废水悬浮固体(SS)浓度保持稳定。3. Reaction box mud pump: quantitatively discharge mud to keep the wastewater suspended solids (SS) concentration in the membrane filtration zone stable.

4、搅拌机：使废水和药剂充分混合，保证钙镁硅等去除率。4. Mixer: fully mix waste water and medicament to ensure the removal rate of calcium, magnesium and silicon.

5、膜池进水泵：加药反应后的废水定量进入膜过滤装置。5. Membrane tank inlet pump: the wastewater after the dosing reaction enters the membrane filtration device quantitatively.

6、膜池：膜过滤装置区6. Membrane tank: membrane filtration device area

7、膜组件：对加药反应后的废水进行固液分离，确保出水达到反渗透进水水质。7. Membrane module: Solid-liquid separation is performed on the wastewater after the dosing reaction to ensure that the effluent reaches the reverse osmosis influent water quality.

8、曝气装置：保证膜过滤区废水的浓度均匀；冲刷膜表面，防止膜污染。8. Aeration device: to ensure uniform concentration of wastewater in the membrane filtration area; flush the membrane surface to prevent membrane pollution.

9、膜池排泥泵：膜组件截留的污泥颗粒排出膜池。9. Membrane tank sludge pump: The sludge particles trapped by the membrane module are discharged from the membrane tank.

10、产水泵：提供跨膜压差，定量出水。10. Water production pump: Provides transmembrane pressure difference and quantitatively discharges water.

11、反洗水箱：可定期配制一定浓度的反洗水。11. Backwash water tank: a certain concentration of backwash water can be prepared regularly.

12、反洗泵：使反洗箱中水反洗膜组件。12. Backwash pump: Backwash the membrane module with water in the backwash tank.

13、清洗系统：清洗膜组件。13. Cleaning system: cleaning membrane components.

与现有技术相比，本发明的技术效果如下：Compared with the prior art, the technical effects of the present invention are as follows:

1、本发明工艺采用一体化反应装置和膜分离装置的组合，应用于高盐水的软化和除硬，工艺流程少。而传统工艺一般采用混合反应+沉淀+粗过滤(砂滤)+超(微)滤工艺组合。1. The process of the present invention adopts a combination of an integrated reaction device and a membrane separation device, and is applied to the softening and hardening of high salt water, and the process flow is small. The traditional process generally uses a combination of mixed reaction + precipitation + coarse filtration (sand filtration) + ultra (micro) filtration.

2、本发明工艺流程比传统工艺大大简化，无需考虑污泥的沉淀分离和多级过滤，设备少，占地面积小，施工工期短，投资成本低。2. The process of the present invention is greatly simplified compared with the traditional process, does not need to consider the sedimentation and separation of sludge and multi-stage filtration, has less equipment, small floor space, short construction period and low investment cost.

3、本发明工艺利用过滤的筛分机理进行固液分离，直接将反应生成的颗粒物截留在膜丝外侧，不需要考虑传统软化工艺(反应-沉淀-过滤-超滤)中沉淀分离的沉降时间及水质波动对沉淀颗粒的影响，工艺运行更加稳定。3. The process of the present invention uses the filtering sieving mechanism for solid-liquid separation, directly trapping the particles generated by the reaction on the outside of the membrane filament, without considering the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) And the impact of water quality fluctuations on the precipitated particles, the process operation is more stable.

4、本发明工艺可以高效去除高盐废水中的硬度及硅含量等，能耗低，处理吨水电耗0.8-1KWH。传统混合反应+沉淀+过滤(砂滤)+超(微)滤的组合工艺的处理吨水电耗1.5KWH，运行能耗也具有较大优势。4. The process of the present invention can efficiently remove the hardness and silicon content in high-salt wastewater, has low energy consumption, and consumes 0.8-1KWH of water and electricity per ton of treatment. The combined process of traditional mixing reaction + precipitation + filtration (sand filtration) + ultra (micro) filtration consumes 1.5 KWH of water and electricity per ton, and the operating energy consumption also has greater advantages.

5、本发明所选用的膜具有以下两个特点：①膜元件材质为PTFE材质，具有很好的耐酸性和耐碱性，可以在1-14的pH任意范围运行，化学加药后无需回调pH，可以直接与膜元件接触；对氯离子浓度无要求，不存在氯离子腐蚀问题。②膜孔径为0.01～0.5um的范围，远远小于软化生成的碳酸钙(20um以上)和氢氧化镁颗粒直径(1-5um)，远远小于钙镁硅酸盐所生成的螯合物的颗粒直径，因此可以利用筛分过滤的原理，直接将反应生成的颗粒物截留在膜丝外侧，不需要考虑传统软化工艺(反应-沉淀-过滤-超滤)中沉淀分离的沉降时间及水质波动对沉淀颗粒的影响。5. The membrane selected in the present invention has the following two characteristics: ①The membrane element is made of PTFE, which has good acid and alkali resistance, and can operate in any range of pH 1-14, and there is no need to call back after chemical dosing pH, can directly contact the membrane element; there is no requirement for chloride ion concentration, and there is no chloride ion corrosion problem. ②The pore size of the membrane is in the range of 0.01～0.5um, which is much smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than that of chelate produced by calcium magnesium silicate. Particle diameter, so the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time and water quality fluctuations in the traditional softening process (reaction-precipitation-filtration-ultrafiltration). The impact of sedimentation particles.

附图说明Description of the drawings

图1为本发明实施例1中高盐废水除硬除硅除浊的处理系统结构示意图。Fig. 1 is a schematic diagram of the structure of a treatment system for removing hard, silicon and turbidity of high-salt wastewater in Example 1 of the present invention.

1反应箱；2加药装置；3反应箱排泥泵；4搅拌机；5膜池进水泵；6膜池；7膜组件；8曝气装置；9膜池排泥泵；10产水泵；11反洗水箱；12反洗泵；13化学清洗系统。1 reaction tank; 2 dosing device; 3 reaction tank mud pump; 4 mixer; 5 membrane tank inlet pump; 6 membrane tank; 7 membrane module; 8 aeration device; 9 membrane tank mud pump; 10 production water pump; 11 Backwash water tank; 12 backwash pump; 13 chemical cleaning system.

具体实施方式detailed description

下面结合附图和具体实施例对本发明进行详细说明。The present invention will be described in detail below with reference to the drawings and specific embodiments.

实施例1Example 1

一种高盐废水除硬除硅除浊的处理系统，参考图1，包括一体化反应装置和膜分离装置，所述一体化反应装置包括反应箱1、用于向反应箱1加入药剂的加药装置2，所述膜分离装置包括膜池6、设置在膜池6中用于对来自反应箱1的混合液进行分离的膜组件7，以及从膜池6引出的产水管线，在产水管线上设置产水泵10，在反应箱1与膜池6之间连接用于使反应箱1中加入药剂反应后的混合液直接进入到膜池6的膜池进水管线，在膜池进水管线上设置膜池进水泵5。A treatment system for removing hard, silicon, and turbidity of high-salt wastewater, referring to FIG. 1, includes an integrated reaction device and a membrane separation device. The integrated reaction device includes a reaction box 1, and is used for adding chemicals to the reaction box 1. Medicine device 2, the membrane separation device includes a membrane tank 6, a membrane module 7 arranged in the membrane tank 6 for separating the mixed liquid from the reaction tank 1, and a water production line drawn from the membrane tank 6, in production The water production pump 10 is installed on the water pipeline, and is connected between the reaction tank 1 and the membrane tank 6 to make the mixed liquid after adding the chemical reaction in the reaction tank 1 directly enter the membrane tank water inlet pipeline of the membrane tank 6, and enter the membrane tank A membrane tank inlet pump 5 is set on the water pipeline.

本实施例中，所述反应箱1内置挡板，将反应箱1内部分隔成多个加药隔间，所述挡板在反应箱1内高低交错排列，形成可以使溶液在反应器内上下折流的通道。加药隔间包括但不仅限于软化药剂加药间、除硅剂加药间。In this embodiment, the reaction box 1 has a built-in baffle, which divides the inside of the reaction box 1 into a plurality of dosing compartments. The baffles are arranged in a staggered arrangement in the reaction box 1 so that the solution can move up and down in the reactor. Baffled channel. The dosing compartment includes but is not limited to the softening agent dosing room and the silicon removal agent dosing room.

本实施例中，所述反应箱1内设置搅拌机4，在反应箱1底部设置反应箱排泥泵3。In this embodiment, a stirrer 4 is provided in the reaction box 1, and a reaction box mud pump 3 is provided at the bottom of the reaction box 1.

本实施例中，所述膜池6内的膜组件7设置一组或多组。In this embodiment, one or more sets of membrane modules 7 in the membrane tank 6 are provided.

本实施例中，所述膜组件7的材质为聚四氟乙烯(PTFE)，具有很好的耐酸性和耐碱性，可以耐受pH为1-14的范围长期运行，化学加药后无需回调pH，可以直接与膜元件接触；同时可以耐受3000ppm以内的次氯酸钠溶液的浸泡。对氯离子浓度无要求，不存在氯离子腐蚀问题。In this embodiment, the material of the membrane component 7 is polytetrafluoroethylene (PTFE), which has good acid and alkali resistance, and can withstand long-term operation in the range of pH 1-14. There is no need for chemical dosing. Adjusting the pH, it can directly contact the membrane element; at the same time, it can withstand the immersion of sodium hypochlorite solution within 3000ppm. There is no requirement for chloride ion concentration and there is no chloride ion corrosion problem.

本实施例中，所述膜组件7孔径为0.01-0.5μm，根据需求选择不公的孔径范围，可以满足多种不同颗粒物粒径的使用要求。膜孔径为0.01～0.5um的范围，远远小于软化生成的碳酸钙(20um以上)和氢氧化镁颗粒直径(1-5um)，远远小于钙镁硅酸盐所生成的螯合物的颗粒直径，因此可以利用筛分过滤的原理，直接将反应生 成的颗粒物截留在膜丝外侧，不需要考虑传统软化工艺(反应-沉淀-过滤-超滤)中沉淀分离的沉降时间及水质波动对沉淀颗粒的影响。In this embodiment, the pore size of the membrane module 7 is 0.01-0.5 μm, and an unfair pore size range is selected according to requirements, which can meet the requirements for the use of various particle sizes. The membrane pore size is in the range of 0.01～0.5um, which is far smaller than the diameter of calcium carbonate (above 20um) and magnesium hydroxide particles (1-5um) produced by softening, and much smaller than the particles of chelate produced by calcium magnesium silicate Therefore, the principle of sieving and filtration can be used to directly trap the particles generated by the reaction on the outside of the membrane. There is no need to consider the sedimentation time of the precipitation separation in the traditional softening process (reaction-precipitation-filtration-ultrafiltration) and the influence of water quality fluctuations on the precipitation The impact of particles.

本实施例中，所述膜组件7的形式包括但不仅限于板式、管式、中空纤维、卷式等。In this embodiment, the form of the membrane module 7 includes, but is not limited to, a plate type, a tube type, a hollow fiber, a roll type, and the like.

本实施例中，所述膜池6底部设置曝气装置8与膜池排泥泵9。曝气装置8主要是混合搅拌作用，使膜池6内污泥处于悬浮状态，浓度均匀，不沉积在膜表面，同时冲刷膜表面，防止膜污染。In this embodiment, the bottom of the membrane tank 6 is provided with an aeration device 8 and a membrane tank mud pump 9. The aeration device 8 is mainly used for mixing and stirring, so that the sludge in the membrane tank 6 is in a suspended state, with a uniform concentration, and does not deposit on the membrane surface, while scouring the membrane surface to prevent membrane pollution.

本实施例中，在所述产水管线上设置反洗系统与化学清洗系统，所述反洗系统包括反洗水箱11以及反洗水箱11与产水管线之间的反洗管线，在所述反洗管线上设置反洗泵12；所述化学清洗系统包括酸计量箱、酸加药泵、碱计量箱、碱加药泵、次氯酸钠计量箱、次氯酸钠加药泵等设备。所述反洗水箱中的反洗水经过反洗泵进入到膜分离装置对膜进行清洗，以保证膜的分离效率。根据需要，反洗水箱中的水可以是产水或者定期配制一定酸、碱和次氯酸钠溶液等进行反洗。In this embodiment, a backwash system and a chemical cleaning system are provided on the water production pipeline. The backwash system includes a backwash water tank 11 and a backwash pipeline between the backwash water tank 11 and the water production pipeline. A backwash pump 12 is provided on the backwash pipeline; the chemical cleaning system includes acid metering tank, acid dosing pump, alkali metering box, alkali dosing pump, sodium hypochlorite metering box, sodium hypochlorite dosing pump and other equipment. The backwash water in the backwash water tank enters the membrane separation device through the backwash pump to clean the membrane to ensure the separation efficiency of the membrane. According to needs, the water in the backwash water tank can be produced water or a certain acid, alkali and sodium hypochlorite solution can be regularly prepared for backwashing.

本实施例还提供基于所述处理系统进行高盐废水除硬除硅除浊的处理工艺，包括以下步骤：This embodiment also provides a treatment process for removing hard, silicon and turbidity from high-salt wastewater based on the treatment system, which includes the following steps:

高盐废水进入反应箱1，根据废水水质和产水要求，通过加药装置2在废水中加入所需药剂，在搅拌作用下药剂与废水充分混合反应产生不同种类的污泥颗粒，包括但不仅限于碳酸钙污泥、氢氧化镁污泥、硅酸盐污泥，进而去除废水中的硬度、二氧化硅、浊度等；The high-salt wastewater enters the reaction tank 1. According to the requirements of wastewater quality and water production, the required agent is added to the wastewater through the dosing device 2. The agent and the wastewater are fully mixed and reacted to produce different types of sludge particles, including but not only Limited to calcium carbonate sludge, magnesium hydroxide sludge, silicate sludge, and then remove the hardness, silica, turbidity, etc. in the wastewater;

污泥颗粒混合液直接进入到膜池6中；在曝气装置的作用下处于悬浮状态、浓度均匀，经过膜组件7的筛分过滤，产水经产水泵10排出膜池6，截留的污泥颗粒经过膜池排泥泵9排出膜池6；所述膜分离装置利用筛分过滤的原理，直接将混合液的污泥颗粒物截留在膜丝外侧，产水回收利用，污泥颗粒外排出膜分离装置。The sludge particle mixture directly enters the membrane tank 6; it is suspended and uniform in concentration under the action of the aeration device. After the screening and filtration of the membrane module 7, the produced water is discharged from the membrane tank 6 through the production water pump 10, and the trapped sewage The sludge particles are discharged from the membrane tank 6 through the membrane tank sludge pump 9; the membrane separation device uses the principle of sieving and filtration to directly trap the sludge particles of the mixed liquid on the outside of the membrane filaments, the produced water is recycled and used, and the sludge particles are discharged outside Membrane separation device.

其中，所述产水满足反渗透进水的要求。所需药剂包括但不仅限于软化药剂、除硅剂，所述软化药剂包括石灰、氢氧化钠、碳酸钠等。所述处理工艺采用连续进出水方式，采用连续排泥或间歇排泥的运行方式。Wherein, the produced water meets the requirement of reverse osmosis water inflow. The required agents include, but are not limited to, softening agents and silicon removal agents, and the softening agents include lime, sodium hydroxide, sodium carbonate and the like. The treatment process adopts a continuous water inlet and outlet mode, and an operation mode of continuous sludge discharge or intermittent sludge discharge.

实施例2Example 2

某煤化工高盐废水中TDS含量为35000mg/L，SiO 2浓度为80mg/L，硬度为5mmol/L左右，属于高盐、高硅、高硬度废水。经使用实施例1中高盐废水除硬除硅除浊的处理工艺处理后，进水SS浓度为1.2～2.5g/L，膜过滤区废水SS浓度浓缩 至15.5～33g/L，浓缩倍数为10～20倍。产水中SiO 2＜18mg/L，硬度＜0.5mmol/L，SDI保持在3～5，浊度＜1NTU，产水可以直接进入到后续反渗透处理工艺。 The high-salt wastewater of a coal chemical industry has TDS content of 35000mg/L, SiO 2 concentration of 80mg/L, and hardness of about 5mmol/L. It belongs to high-salt, high-silicon, and high-hardness wastewater. After using the high-salt wastewater treatment process for removing hard, silicon and turbidity in Example 1, the influent SS concentration is 1.2~2.5g/L, the SS concentration of wastewater in the membrane filtration zone is concentrated to 15.5~33g/L, and the concentration factor is 10. ~20 times. The SiO 2 in the product water is less than 18mg/L, the hardness is less than 0.5mmol/L, the SDI is maintained at 3 to 5, and the turbidity is less than 1NTU, and the product water can be directly fed into the subsequent reverse osmosis treatment process.

实施例3Example 3

某高盐废水中TDS含量为45000mg/L，SiO 2浓度为150mg/L，硬度为8mmol/L左右，属于高盐、高硅、高硬度废水。经使用实施例1中高盐废水除硬除硅除浊的处理工艺处理后，产水SiO 2＜15mg/L，硬度较小，SDI范围3～4，浊度＜0.5NTU。产水进入到后续反渗透处理工艺，反渗透系统的运行稳定性良好，清洗周期稳定＞1.5个月。 The content of TDS in a certain high-salt wastewater is 45000mg/L, the concentration of SiO 2 is 150mg/L, and the hardness is about 8mmol/L. It belongs to high-salt, high-silicon, and high-hardness wastewater. After using the high-salt wastewater in Example 1 to remove hard and silicon and remove turbidity, the water produced has SiO 2 <15 mg/L, low hardness, SDI range of 3 to 4, and turbidity <0.5NTU. The product water enters the subsequent reverse osmosis treatment process, the operating stability of the reverse osmosis system is good, and the cleaning cycle is stable> 1.5 months.

实施例4Example 4

某高盐废水中TDS含量为50000mg/L，SiO 2浓度为400mg/L，硬度为10mmol/L左右，属于高盐、高硅、高硬度废水。经使用实施例1中高盐废水除硬除硅除浊的处理工艺处理后，产水中废水的SiO 2＜30mg/L，硬度＜0.8mmol/L，SDI≤5，浊度保持在0.5NTU以下。 The TDS content in a certain high-salt wastewater is 50000mg/L, the SiO 2 concentration is 400mg/L, and the hardness is about 10mmol/L. It belongs to high-salt, high-silicon and high-hardness wastewater. After using the high-salt wastewater in Example 1 to remove hard and silicon and remove turbidity, the SiO 2 of the produced water wastewater is less than 30 mg/L, the hardness is less than 0.8 mmol/L, the SDI is less than or equal to 5, and the turbidity remains below 0.5 NTU.

上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is for the convenience of those skilled in the art to understand and use the invention. Those skilled in the art can obviously make various modifications to these embodiments and apply the general principles described here to other embodiments without creative work. Therefore, the present invention is not limited to the above-mentioned embodiments. According to the disclosure of the present invention by those skilled in the art, all improvements and modifications made without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (10)

一种高盐废水除硬除硅除浊的处理系统，其特征在于，包括一体化反应装置和膜分离装置，所述一体化反应装置包括反应箱、用于向反应箱加入药剂的加药装置，所述膜分离装置包括膜池、设置在膜池中用于对来自反应箱的混合液进行分离的膜组件，以及从膜池引出的产水管线，在反应箱与膜池之间连接用于使反应箱中加入药剂反应后的混合液直接进入到膜池的膜池进水管线。A treatment system for removing hard, silicon, and turbidity of high-salt wastewater, which is characterized by comprising an integrated reaction device and a membrane separation device. The integrated reaction device includes a reaction box and a dosing device for adding chemicals to the reaction box The membrane separation device includes a membrane tank, a membrane module arranged in the membrane tank for separating the mixed liquid from the reaction tank, and a water production pipeline drawn from the membrane tank, which is connected between the reaction tank and the membrane tank for The mixed solution after adding the chemical reaction in the reaction box directly enters the membrane tank water inlet pipeline of the membrane tank. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述反应箱内置挡板，将反应箱内部分隔成多个加药隔间，所述挡板在反应箱内高低交错排列，形成可以使溶液在反应器内上下折流的通道。The treatment system for removing hard, silicon, and turbidity of high-salt wastewater according to claim 1, wherein the reaction box has a built-in baffle that divides the inside of the reaction box into a plurality of dosing compartments, and the block The plates are arranged in a staggered arrangement in the reaction box, forming channels that can make the solution baffle up and down in the reactor. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述反应箱内设置搅拌机，在投加药剂后充分混合搅拌，使生成颗粒物不致沉淀，并且进水在反应箱中有足够的停留时间，使化学反应完全发生在反应箱中，在反应箱底部设置反应箱排泥泵。The treatment system for removing hard, silicon and turbidity of high-salt wastewater according to claim 1, characterized in that a mixer is installed in the reaction box, and after adding the agent, it is fully mixed and stirred to prevent the generated particles from being precipitated, and The influent water has enough residence time in the reaction box to make the chemical reaction completely occur in the reaction box, and the reaction box mud pump is set at the bottom of the reaction box. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述膜池内的膜组件设置一组或多组。The treatment system for removing hard, silicon and turbidity of high-salt wastewater according to claim 1, wherein one or more groups of membrane modules are arranged in the membrane tank. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述膜组件的材质为聚四氟乙烯，耐受pH为1-14的范围长期运行，同时可以耐受3000ppm以内的次氯酸钠溶液的浸泡。The treatment system for removing hard, silicon, and turbidity in high-salt wastewater according to claim 1, wherein the membrane module is made of polytetrafluoroethylene, which can withstand long-term operation in the range of pH 1-14, At the same time, it can withstand the immersion of sodium hypochlorite solution within 3000ppm. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述膜组件孔径为0.01-0.5μm。The treatment system for removing hard, silicon and turbidity of high-salt wastewater according to claim 1, wherein the pore size of the membrane module is 0.01-0.5 μm. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，所述膜池底部设置曝气装置与膜池排泥泵，使污泥在膜池中处于悬浮状态，同时，不会在膜组件的膜丝表面附着。A treatment system for removing hard, silicon, and turbidity in high-salt wastewater according to claim 1, wherein an aeration device and a sludge pump in the membrane tank are arranged at the bottom of the membrane tank to make the sludge in the membrane tank In a suspended state, at the same time, it will not adhere to the membrane filament surface of the membrane module. 根据权利要求1所述的一种高盐废水除硬除硅除浊的处理系统，其特征在于，在所述产水管线上设置反洗系统与化学清洗系统，所述反洗系统包括反洗水箱以及反洗水箱与产水管线之间的反洗管线，在所述反洗管线上设置反洗泵；The treatment system for removing hard, silicon and turbidity of high-salt wastewater according to claim 1, wherein a backwashing system and a chemical cleaning system are provided on the water production pipeline, and the backwashing system includes backwashing. The water tank and the backwash pipeline between the backwash water tank and the water production pipeline, and a backwash pump is arranged on the backwash pipeline; 所述化学清洗系统包括酸计量箱、酸加药泵、碱计量箱、碱加药泵、次氯酸钠计量箱、次氯酸钠加药泵。The chemical cleaning system includes an acid metering box, an acid dosing pump, an alkali metering box, an alkali dosing pump, a sodium hypochlorite metering box, and a sodium hypochlorite dosing pump. 基于权利要求1-8中任一项所述处理系统进行高盐废水除硬除硅除浊的处 理工艺，其特征在于，包括以下步骤：The treatment process for removing hard, silicon and turbidity from high-salt wastewater based on the treatment system of any one of claims 1-8 is characterized in that it comprises the following steps: 高盐废水进入反应箱，通过加药装置在废水中加入所需药剂，药剂与废水充分混合反应产生不同种类的污泥颗粒；The high-salt wastewater enters the reaction tank, and the required agent is added to the wastewater through the dosing device, and the agent and the wastewater are fully mixed and reacted to produce different types of sludge particles; 污泥颗粒混合液直接进入到膜池中；在曝气装置的作用下处于悬浮状态、浓度均匀，经过膜组件的筛分过滤，产水排出膜池，截留的污泥颗粒排出膜池；The sludge particle mixture directly enters the membrane tank; it is in a suspended state and uniform concentration under the action of the aeration device, and is filtered by the membrane module, the product water is discharged from the membrane tank, and the intercepted sludge particles are discharged from the membrane tank; 所述产水满足反渗透进水的要求。The produced water meets the requirement of reverse osmosis water inflow. 根据权利要求9所述高盐废水除硬除硅除浊的处理工艺，其特征在于，所述处理工艺采用连续进出水方式，采用连续排泥或间歇排泥的运行方式。The treatment process for removing hard, silicon and turbidity of high-salt wastewater according to claim 9, characterized in that the treatment process adopts a continuous water inlet and outlet mode, and an operation mode of continuous sludge discharge or intermittent sludge discharge.
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